Geminal dehydrogenation of ether and amine C(sp3)H2 groups by electron-rich Ru(ii) and OsElectronic supplementary information (ESI) available: crystallographic data, fractional coordinates and isotropic thermal parameters, anisotropic thermal parameters, and bond distances and angles. See http://www.rsc.org/suppdata/nj/b2/b200168n/

Coordinatively Unsaturated Cationic and Zwitterionic [Cp*Ru(κ2‐P,N)] Complexes: Ligand‐Assisted Double‐Geminal CH Bond Activation and Reversible α‐H Elimination at Ruthenium

“…The identification of 8 b as a hydridocarbene complex was based in part on the observation of 1 H NMR signals at δ =12.1 and −12.4 ppm, as well as a 13 C NMR resonance at δ =244.1 ppm; the structure of 8 b was subsequently confirmed by X‐ray diffraction analysis (Figure 1). 8b,d The contracted RuC27 (1.886(2) Å) and NC27 (1.374(3) Å) distances in 8 b are comparable to some other N‐stabilized RuC fragments 12b–d. These interatomic distances, the short NC2 distance (1.384(3) Å; cf.…”

Carbene–Transition Metal Complexes Formed by Double CH Bond Activation

“…It is formed as the major product from [OsH 3 Cl(PiPr 3 ) 2 ] and CH 2 =CHtBu (ratio 1:2) in neat THF, and it has been characterized by 1 H and 31 P NMR spectroscopy. [58] [58] The third recent achievement of Whited and Grubbs marks an important extension of their work on atom-and group-transfer metathesis. Taking the isoelectronic nature of CO and N 2 into account, it was found that the iridium(I) oxocarbene 63 not only reacted with isocyanates RNCO but also with organic azides RN 3 .…”

“…This 14-electron species, generated from the corresponding dimer, reacted with THF, dioxolane, and pyrrolidine to give the five-coordinate ruthenium(II) complexes 78, 79, and 80 a,b, which contain cyclic oxo-and aminocarbene ligands (Scheme 26). [58,59] The six-membered counterparts 1,4-dioxane, 1,3,5-trioxane, and piperidine did not react similarly and failed to produce the ruthenium carbene compounds upon reaction with [RuH(Cl)(PiPr 3 ) 2 ] 2 . An analogue of 80 a with PCy 3 instead of PiPr 3 as phosphine ligand was obtained from [RuH(H 2 )Cl(PCy 3 ) 2 ] and excess pyrrolidine in the presence of CH 2 =CHtBu.…”

Synthesis of a ruthenium bis(diisopropylamino(isocyano)borane) complex from the activation of an amino(cyano)borane

“…The N3-C8 (6a: 1.184(5); 6b: 1.186(5)) and N1-C1 (6a: 1.178(5); 6b: 1.173(5)) bond lengths are however similar, and are set at the upper limit for a coordinated isocyano CN group when compared with those in the only two reported crystal structures R 2 R 1 BNCCr(CO) 5 [29][30][31][32] They both exhibit a partial C-N triple bond character. The isocyano carbon ruthenium distances Ru1-C1 and Ru1-C8 are shorter than the sum of the single-bond covalent radii (2.00 Å), 33 thus suggesting a partially double bond character [34][35][36][37][38][39] as a result of the metal-to-ligand π-back bonding that takes place more effectively towards the isocyanoborane trans to the cyano group and involving a deviation from linearity of the CN-B axis at the N atom. The nitrogen boron distances in 6a/6b (1.335 < NB < 1.495 Å) are in the range of values observed for amino substituted trigonal-planar boron groups.…”